Purification of hydrocarbons



UNITED s'rAr-Es PATENT OFFICE.

OSCAR E. BRAN SKY, OF WHITING, INDIANA, ASSIGHOR TO STANDARD OIL COMPANY,

NHITING, IN'DIAINA, A CORPORATION OF INDIANA.

PITRIFICATION OI? HYDROCARBONS.

No Drawing.

T 0 all -w lzmn it may concern:

Be it known tl18.t" ];1i OSGAR E. BRANsKY,'a citizen of the United States, residing at Vhiting, in the county of Lake and State of Indiana, have invented a new and useful Improvement in the Purification of Hydrocarbons, of which the following is a specifi-- or fuming sulfuric it has been found that sulfonated compounds are formed which have a preferential solubility in water in the presence of oils. These compounds which appear are found in the acid sludge after the acid treatment and may be removed therefrom in a'state of purity suitable for commercial purposes by first extracting from the sludge the oil-soluble sulfonic acids present by means of a light hydrocarbon oil, and subsequently removing the excess of acid from the remaining sludge by boiling with water and drawing off the dilute acid layer which settles out. The sludge contains the Watersoluble sulfonated compound or acids, which, by reason of their color, are designated as the green sulfonic acids. The process for their preparation has been more fully described in the prior application of Robert E. Humphrey's, Francis M. Rogers and myself, filed October 25. 1918, Serial No. 259,689. In the present process these green sulfonic acids or their alkali metal salts are utilized as hereinafter set forth.

In the acid re-tining of hydrocarbons by means of concentrated or fuming sulfuric acid. a certain portion of the sulfonated compounds, principally sulfo-acids, remain in solution in the oil on separation of the acid sludge. These sulfonated compounds known as the mahogany sulfonic acids." may not be removed from the oil by means of water either in the form of acids or soaps Specification of Letters Patent.

to be largely sulfonic acids,

if convenient, over night.

Patented Nov. 8, 1921.

Application filed November 26, 1919. Serial No. 340,883.

resulting from their neutralization by a suitable alkali, such as soda ash, as they cause the formation of emulsions of water and oil which cannot readily be broken down. It has now been found, however, that by aqueous solutions of the green sulfo compounds (which term applies to both the acid compounds and their soaps) the oil-soluble sulfonated compounds may be extracted from the refined oils without the formation of stable emulsions.

To illustrate the practice of the present invention, for example, in the treatment of a lubricating oil, such as solar red oil, a

suitable volume of the oil may be treated with sulfuric acid in a 66 B. solution in the proportion of about t} lb. of acid to each gallon of oil. The acid may be added in one or more successive dumps, the mass being agitated after each dump.v After separation the sludge is drawn off, and may be treated in any desired manner for the recovery of acid, green sulfonic acids, etc. The oil, which contains the mahogany sulfonic acids, may then be neutralized, preferably with a solution of alkali metal compound, such as a 15 B. solution of sodium carbonate. The excess of alkali frequently separates as a clear solution, and may be removed, if desired, leaving the soaps of the mahogany acids in solution in the oil. In either case the oil is then heated to about 130 F. and 1 to 10% of'its volume of an aqueous solution containing 10 to 15% of the sodium salt of green sulfonic acids is of water, for example, to about 180 F., and

is permitted to stand for several hours, or

cation takes place, and the aqueous solution, containing t e mahogany sulfonated compounds as well as the green compounds, is drawn off. It may be utilized in any desired manner, for example, as a detergent, fat-splitting reagent, or the like. The sepa- Perfect stratifirated oil is washed with 'water once or I twice, and may be subjected to any desired further treatment.

It is apparent that the invention may likewise be applied to the separation of the oildissolved sulfonic acids by adding to the aqueous solution of salts of the green sulfonic acids the alkali necessary for the neu- )tralization of the acids contained in the oil after its initial separation from the acid sludge. The removal of the oil-dissolved sulfonated compounds will then take place simultaneously with the neutralization of the acids present in the oil.

The solution of the green s'ulfonic acids possesses inlike manner with the solution of their salts the capacity to remove the oil dissolved sulfonated compounds from the acid treated oil without the formation of stable emulsions. Hence an aqueous solution of the green sulfonic acids may be used for washing the oil directly after its separation from the acid sludge, thereby removing the oil dissolved sulfonated compounds, and the treated oil may be subsequently neutralized or subjected to other treatment in any desired manner.

f desired, the solution of green sulfo compounds utilized may contain a greater or less amount of the mahogany compounds Where it is found unnecessary or undesirable to remove the latter by extraction with oil as hereinbefore described.

Although my invention has been hereinbefore described in connection with a specific example of its application, it is not intended thatthe details presented are to be regarded as limitations upon the scope of the invention, except in so far as included in the accompanying claims.

I claim:

1. In the process of purifying acid-treated hydrocarbon, the step which consists in extracting such oils with an aqueous solution of green sulfonated mineral oil compounds,'thereby removing the oil-dissolved sulfonated compounds.

2. The process of refining oil which consists in treating oil with sulfuric acid, separating the oil from the acid sludge and treat-' ing the separated oil with an aqueous solu- .tion of green sulfonated mineral oil compounds in the presence of a neutralizing agent, thereby removing the oil-dissolved sulfonated compounds.

3. The process of refining oil which consists in treating oil with sulfuric acid, separating the oil from the acid sludge, neutralizing the oil, and agitating the neutralized oil with an aqueous solution of the alkali metal salts of green mineraloil sulfonic acids.

and separating the treated oil from the aqueous solution.

4. The process of refining oil which consists in treating oil with sulfuric acid, separating the oil from the acid sludge, neutralizing the oil with soda and extracting the oil with a 1015% aqueous solution of sodium salts of green mineral oil sulfonic acids.

5. The process which consists in extracting neutralized acid treated hydrocarbons with neutralized green mineral oil sulfonic acids in aqueous solution.-

6. The process of preventing emulsifica tion of oils with Water which consists in preliminarily adding to the latter green sulfocompounds of mineral oils.

7. The method of treating mineral oil, as petroleum or petroleum products, which consists in washing the same without substantial emulsification thereof with an aqueous solution of sludge sulfonates.

8. The process of preventing emulsification of oils with water which consists in preliminarily addin to the latter sulfo-compounds of minera oil acid sludge.

9. In the process of hydrocarbon, the ste which consists in extracting such oils with an aqueous solution of the alkali metal salts of mineral oil acid sludge sulfonic acids.

10. In the process of purifying acid treated hydrocarbons, the step which consists in extracting such oils with an aqueous solution containing water soluble sulfo-compounds derived from the treatment of hydrocarbon oil with fuming sulfuric acid, thereby removing the oil dissolved sulfonated compounds.

11. The method of washing mineral oil of the character of petroleum or petroleum products, which consists in agitating said oil, while maintained at suitable viscosity, in the presence of water and of water soluble sulfo compounds derived from the treatment of mineral oils with strong sulfuric acid, the proportions of water and sulfo compounds being such as to prevent emulsification of the oil and cause removal therefrom into the water of the emulsification inducing contents.

OSCAR E. BRANSKY.

purifying acid-treated 

